DE1643215B2 - PROCESS FOR PRODUCING BETA-THIOAETHERTHIOCARBONIC ACID ESTERS - Google Patents

Description

SR It's surprising that the Trithio-o-ants-

j acid esters, although they are much less reactive than

X - CH - CH ₄ - CO - SR are the corresponding oxygen o-esters, among the

to applied conditions so smoothly with ketene to the

in which X = —SR or CH ₂ CO - SR and R react a corresponding carboxylic acid derivative,
optionally substituted alkyl radical is d a- The products prepared according to the invention are suitable

characterized in that one is used, for example, as plasticizers and stabilizers, Trithio-o ^ formic acid esters of the formula z. B. for polyvinyl chloride and polyvinyl acetate, as

"", _SR . 15 pesticides as well as for the production of

* ■ " pharmaceutically active substances,

in the presence of a strongly acidic catalyst. .

at temperatures between -20 and 90 ^° C., example 1

optionally in the presence of a solution 40 g of trithio-o-formic acid triethyl ester were in

means, dissolved with ketene ao 350 ml of TetraäthylsUan and in the presence of

0.7% hexafluorophosphoric at - 50 ⁰ C in a

CH ₂ = C = O autoclave mixed with 30 g of ketene. The reaction

implements. duration was 16 hours, the reaction temperature

5 to 10 ^° C. The reaction mixture was distilled

as worked up.

Yield of / 9-ethylthioether-dithioglutaric acid diethyl ester: 50% of theory.

Triethyl formate forms in the presence of zinc boiling point: 96 to 98 ° C / 0.05 Torr.

Chloride with ketene in 92% yield den ß, ß-Di · . .

ethoxypropionic acid ethyl ester (F. S ο r m and J. 30 example /

Smit, Chem. Listy, 47: 413 (1953). The latter rea- 40g trithio-o-formic acid triethyl ester and 2g

Yielded under the same conditions ^ in only 22% boron trifluoride dietherate were yielded in 150 ml of methylene with ketene further dissolved to the ethoxyglutaric acid chloride and at room temperature with 18 g diethyl ester. Keten treated. The contained in the reaction mixture

There has now been a process for the preparation of 35 tene catalyst with aqueous sodium acetate-thioether thiocarboxylic acid esters the formula solution neutralized and the organic layer in

High vacuum fractionated. The yield of /? - ethyl

^s ^ thioether-dithioglutaric acid diethyl ester was 55%

I the theory. In addition, 17% / °, / S-Di- (thio-

X - CH - CH ₂ - CO - SR 40 ethyl ether) propionic acid thioethyl ester.

Boiling point: 104 to 108 ° C / 0.16 Torr.

in which X = - SR or CH ₂ CO-SR and R a.

optionally substituted alkyl radical is found. Example 3

The process is characterized in that 35 g of trithio-o-formic acid triethyl ester and 1.5 g

a trithio-o-formic acid ester of the formula 45 hexafluorophosphoric acid were dissolved in 350 ml of methylene

"", _ _R. chloride and dissolved in the autoclave at 5 ⁰ C with ketene

'' ^s treated and the reaction mixture treated by distillation

in the presence of a strongly acidic catalyst when cleaning.

Temperatures between -20 and 9O ⁰ C, gegebenen- The yield of / J-Ätbylthioäther-dithioglutarsäure-

if in the presence of a solvent, diethyl ester with ketene 50 was 87% of theory.

CH ₂ = C = O Example 4

implements. 50 g of trithio-o-formic acid tributyl ester were

As trithio-o-formic acid esters, example 1 in TetraäthylsUan and in counter-

admits those with a carbon number up to 12 in the 55 waiting of hexafluorophosphoric acid as a catalyst

Aikylrest, for example trithio-o-formic acid tri- reacted in the autoclave at 5 to 10 ⁰ C with ketene,

methyl ester, trithio-ο-formic acid triethyl ester. Work-up was carried out as in Example 1

Trithio-ο-formic acid tributyl ester, Trithio-o-amei '. 10% / S, jS * DHthiobutyl-

tridodeeyl sensate, trithio-0-formic acid tri-ether) propionic acid thiobutyl ester, boiling point: 148

benzyl ester. Trithio-o-formic acid ester with alkyl 60 to 152 ° C / 0.12 Torr, and 55% jS-butylthioether ^ di-

residues that have a higher carbon number than 12 dibutyl thioglutarate, boiling point: 186 to 189 ° C /

wise, can also be used, require 0.13 torr, extracted,

but extreme reaction conditions. . ·, E

Suitable acidic catalysts are mineral acids, Example 5

Such as phosphoric acid, fluorophosphorus-65 40 g trithio-o-formic acid tridodecyl ester and 2 g

acids such as hexafluorophosphoric acid or Friedel - boron trifluoride etherate were dissolved in 160 ml of methylene

CraftS 'catalysts, such as. B. boron trifluoride etherate, dissolved chloride and treated with ketene ^{at 4 0 C,}

^ inkchloride, aluminum chloride. After neutralization with aqueous sodium

acetaüösung the reaction mixture with water ester and ß, ß - Di - (thiododecyMfher) .; ■? propionic acid

washed and yarn solvent freed the addodecyl thioester.

remaining crystals had a melting point yield: 77% of theory.

from 30 to 31 ° C. It was a mixture. The structures were determined by JR spectroscopy

from / J-Dodecylthioäther-dithipglutarsäuredidodecyl- 5 secures

Claims (1)

Furthermore, with the patent claim according to the invention: drive, if necessary by choosing the starting material and the implementation conditions (catalog Process for the production of ^ -Thioäther ^ thio- lysator, solvent, temperature, pressure), the carboxylic acid esters of the formula 5 Addition of one or two molecules of ketene the trithio-o-formic acid ester can be achieved.